Photoredox

Dual Nickel-Photoredox Catalysis Enables Unprecedented C-H Functionalization

Context

Direct functionalization of C-H bonds represents one of the most sought-after transformations in organic synthesis, yet traditional methods often require harsh conditions or prefunctionalized substrates. The merger of transition metal catalysis with photoredox catalysis has emerged as a powerful strategy, but achieving high selectivity in complex molecular settings remains challenging.

What's New

This work introduces a dual nickel-photoredox catalytic system that operates under visible light irradiation at room temperature. The key innovation lies in the precise temporal control of radical generation and nickel oxidation states, enabled by an iridium-based photocatalyst. The methodology demonstrates exceptional functional group tolerance and can be applied to complex pharmaceutical scaffolds, achieving regioselectivity that was previously unattainable.

Why It Matters

This advance significantly lowers the barrier for late-stage functionalization in drug discovery, allowing medicinal chemists to rapidly generate analogs without multi-step protecting group strategies. The mild conditions and broad substrate scope suggest immediate applications in industrial settings. Beyond pharmaceuticals, this catalytic platform could streamline syntheses of agrochemicals and advanced materials.

Limitations & Open Questions

The current system requires expensive iridium photocatalysts and shows moderate efficiency with electron-deficient heterocycles. Scale-up beyond gram quantities has not been demonstrated, and the mechanistic details of the nickel-photoredox interplay require further investigation. Catalyst loading remains relatively high (5-10 mol%), presenting opportunities for optimization.
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References

Nature Chemistry (2023)

DOI: 10.1038/s41557-023-01234-5

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